Aldehyde composition

Abstract

Provided is an aldehyde composition that contains an aldehyde represented by formula (1) and an aldehyde represented by formula (2). The mass ratio of the aldehyde represented by formula (1) and the aldehyde represented by formula (2), (1) / (2), is 96 / 4 to 99.97 / 0.03.

Description

[Technical field]

[0001] The present invention relates to an aldehyde composition, a method for producing the same, and a fragrance composition containing the aldehyde composition. [Background technology]

[0002] It is known that some aldehydes, 3-(alkylphenyl)-2-alkylpropanals, are useful as raw materials for compounded fragrances. For example, Non-Patent Document 1 describes that 3-(p-tert-butylphenyl)-2-methylpropanal (p-tert-butyl-α-methylhydrocinnamic aldehyde, lilial), which has a lily of the valley-like fragrance, 3-(p-isopropylphenyl)-2-methylpropanal (cyclamen aldehyde), which has a melon- or cucumber-like fragrance and lily of the valley-like fragrance, and 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (helional), which has a sweet heliotrope and anise-like floral scent, are useful as blended fragrance raw materials.

[0003] Furthermore, Patent Document 1 discloses novel aromatic compounds such as 3-(5-tert-butyl-2-methyl-1-phenyl)propanal as compounds having advantageous odor characteristics in terms of oxidation stability and fragrance tenacity. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Genichi Indo, "Revised and expanded edition of synthetic fragrances: chemistry and product knowledge", 1996, pp. 213-215, 228, Chemical Daily Press [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-330653 Summary of the Invention

Problems to be Solved by the Invention

[0006] In particular, floral-based fragrances and compounded fragrances are used in various fields such as fragrance products, cosmetics, detergents, sanitary products, sundries, pharmaceuticals, and foods. In order to enhance the value of these products, new scents are being developed, and there is a demand for fragrances with new scents. Therefore, an object of the present invention is to provide an aldehyde composition having a fresh marine-like floral and green-like scent, being useful as a fragrance, and further being useful as a raw material for compounded fragrances.

Means for Solving the Problems

[0007] The present inventors synthesized and blended various aldehydes and compositions containing a plurality of them, and evaluated their aromas. As a result, they found that specific aldehydes and compositions containing them have excellent scents and are excellent as raw materials for compounded fragrances, and thus completed the present invention.

[0008] That is, the present invention is as follows. [1] An aldehyde composition containing an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) and the aldehyde represented by formula (2) is 96 / 4 to 99.97 / 0.03.

Chemical formula

Chemical formula

[0009] According to the present invention, it is possible to provide an aldehyde composition having a fresh marine-like floral and green-like fragrance, which is useful as a fragrance and further useful as a blending fragrance raw material. [Modes for Carrying Out the Invention]

[0010] Hereinafter, in this specification, the description of "XX to YY" means "XX or more and YY or less".

[0011] [Aldehyde Composition] The aldehyde composition of the present invention contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), and the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) and the aldehyde represented by formula (2) is 96 / 4 to 99.97 / 0.03. [Chemical formula]

[0012] [Aldehyde Represented by Formula (1)] The aldehyde represented by formula (1) contained in the aldehyde composition of the present invention is 3-(3,4-dimethylphenyl)-2-methylpropanal. The aldehyde represented by formula (1) has a marine-like floral fragrance. The aldehyde represented by formula (1) is also useful as a fragrance and as a blending fragrance raw material.

[0013] [Aldehyde Represented by Formula (2)] The aldehyde represented by the formula (2) contained in the aldehyde composition of the present invention is 3-(2,3-dimethylphenyl)-2-methylpropanal. By containing the aldehyde represented by the formula (2) in the aldehyde composition of the present invention, the fresh marine feeling is remarkably improved.

[0014] <Composition, etc. of aldehyde composition> The total content of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) in the aldehyde composition of the present invention is preferably 95% by mass or more, more preferably 96% by mass or more, and still more preferably 97% by mass or more. There is no limitation on the upper limit value, and it may be 100% by mass or less.

[0015] The mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) in the aldehyde composition of the present invention is 96 / 4 to 99.97 / 0.03, more preferably 97 / 3 to 99.9 / 0.1, and still more preferably 98 / 2 to 99.5 / 0.5. When the mass ratio of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) is within the above range, the aldehyde composition of the present invention has a floral and green-like fragrance with a particularly fresh marine feeling.

[0016] The content of the aldehyde represented by the formula (1) in the aldehyde composition of the present invention is preferably 96% by mass or more, more preferably 97% by mass or more, still more preferably 98% by mass or more, and preferably 99.97% by mass or less, more preferably 99.9% by mass or less, and still more preferably 99.5% by mass or less. The content of the aldehyde represented by the formula (2) in the aldehyde composition of the present invention is preferably 0.03% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably 4% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.

[0017] The aldehyde composition of the present invention may contain an unsaturated aldehyde represented by the following formula (5), but preferably contains as little as possible, more preferably 2% by mass or less, still more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably does not contain it. The unsaturated aldehyde represented by formula (5) is 3-(3,4-dimethylphenyl)-2-methylpropenal. By substantially not containing the aldehyde represented by formula (5), the aldehyde composition of the present invention will have a fresher scent.

Chemical formula

[0018] The aldehyde composition of the present invention may contain an alcohol represented by the following formula (6). The alcohol represented by formula (6) is 3-(3,4-dimethylphenyl)-2-methylpropanol.

Chemical formula

[0019] When the aldehyde composition of the present invention contains the alcohol represented by formula (6), the content of the alcohol represented by formula (6) in the composition is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and preferably 3% by mass or less, more preferably 1% by mass or less. By containing a small amount of the alcohol represented by formula (6), the aldehyde composition of the present invention can impart a more marine feeling to the scent.

[0020] The aldehyde composition of the present invention having the above composition has a fresh, marine-like, floral and green scent, and is thus useful as a fragrance. It is also useful as a raw material for a compounded fragrance (fragrance composition) as described below, and can be used as a fragrance component for various products.

[0021] [Perfume composition] The perfume composition of the present invention contains the aldehyde composition described above. That is, the perfume composition of the present invention contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), and the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) and the aldehyde represented by formula (2) is 96 / 4 to 99.97 / 0.03, and contains an aldehyde composition. When the aldehyde composition is blended into a compounded perfume, the floral feeling and heliotrope-like sweetness are enhanced. [Chemical formula] Furthermore, the perfume composition of the present invention may contain an alcohol represented by the following formula (6). [Chemical formula] Furthermore, the aldehyde composition of the present invention preferably does not substantially contain an unsaturated aldehyde represented by formula (5). [Chemical formula]

[0022] The content of the aldehyde composition in the perfume composition of the present invention may be appropriately adjusted according to the type of the perfume composition, the type of the target fragrance, the strength of the fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass.

[0023] In the perfume composition of the present invention, perfume ingredients that can be used in combination with the aldehyde composition include, but are not limited to, the following. For example, surfactants such as polyoxyethylene lauryl sulfate ether; solvents such as dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate; hydrocarbons such as limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene; alcohols such as linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, β-phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexanemethanol, 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, isocamphylcyclohexanol, 3,7-dimethyl-7-methoxyoctan-2-ol; phenols such as eugenol, thymol, and vanillin;Esters such as linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyl acetate, bornyl acetate, isobornyl acetate, o-t-butylcyclohexyl acetate, p-t-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate, allylcyclohexyl propionate, ethyl 2-cyclohexylpropionate, benzyl propionate, citronellyl butyrate, dimethylbenzylcarbinyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tiglate, cis-3-hexenyl tiglate, methyl jasmonate, methyl dihydrojasmonate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenylglycidate, methyl anthranilate, furfate; Aldehydes such as n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, 2-cyclohexylpropanal, p-t-butyl-α-methylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde, p-ethyl-α,α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, piperonal, α-methyl-3,4-methylenedioxihydrocinnamic aldehyde;Ketones such as methyl heptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amyl cyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methyl cyclopentenolone, rose ketone, γ-methyl ionone, α-ionone, carvone, menthone, borneol, nutkatone, benzyl acetone, anisyl acetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, civetone, cyclopentadecanone, cyclohexadecenone; Acetals and ketals such as acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, ethyl acetoacetate ethylene glycol ketals; Ethers such as anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan; Nitriles such as citronellyl nitrile; Lactones such as γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettolide, ethylene brassylate, 11-oxahexadecanolide; Other fragrance substances such as natural essential oils and natural extracts of orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, hinoki, vetiver, patchouli, labdanum, etc. The other fragrance substances may be used alone or in combination of two or more.;

[0024] For imparting fragrance and improving the fragrance of the object to be blended, the fragrance composition of the present invention can be used as a fragrance component in various products such as cosmetics, health and hygiene materials, sundries, beverages, foods, quasi-drugs, pharmaceuticals, etc. The perfume composition of the present invention can be used, for example, as a fragrance component in fragrance products such as perfumes and colognes; hair cosmetics such as shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades, and sprays; skin cosmetics such as lotions, serums, creams, emulsions, packs, foundations, powders, lipsticks, and makeup cosmetics; hygiene products such as dishwashing detergents, laundry detergents, household detergents, glass cleaners, softeners, bleaches, air fresheners, and insecticides; quasi-drugs such as toothpastes, mouthwashes, bath salts, antiperspirants, and perm agents; sundries such as paper products; pharmaceuticals; and foods.

[0025] The content of the perfume composition of the present invention in the above products may be appropriately adjusted according to the strength of the fragrance required for each product, etc., and is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass.

[0026] Also, the perfume composition according to another embodiment of the present invention contains the aldehyde represented by the above formula (1). The aldehyde represented by the above formula (1) is also useful as a perfume, and the content of the aldehyde represented by the above formula (1) in the perfume composition is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass. Examples of perfume components that can be used in combination with the aldehyde represented by the above formula (1) include those described above. Furthermore, the content of the perfume composition in these products is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, respectively.

[0027] [Method for producing aldehyde and method for producing aldehyde composition] The aldehyde constituting the aldehyde composition of the present invention may be obtained by any production method, but preferably by a production method having an aldol condensation step of aldol-condensing dimethylbenzaldehyde represented by the following general formula (3) and propionaldehyde, and a hydrogenation step in this order to obtain an aldehyde represented by the following general formula (4). [Chemical formula]

[0028] As the aldehydes constituting the aldehyde composition of the present invention, there are at least the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2). When these are produced by the above production method, the reaction is represented by the following formula. The present production method will be described below.

Chemical formula

[0029] The aldehyde composition of the present invention contains the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) with the mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) being 96 / 4 to 99.97 / 0.03. After obtaining the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) by the method of the above formula respectively, these may be mixed and adjusted to the above mass ratio, or they may be mixed at the stage of the above raw materials and intermediates and adjusted to the above mass ratio. Particularly, when a commercial product of 3,4-dimethylbenzaldehyde represented by the formula (3a) as a raw material contains 2,3-dimethylbenzaldehyde represented by the formula (3b), and if these are used as raw materials, and when the mass ratio [(1) / (2)] of the obtained final product is included in the above range, it is simple and preferable to use the commercial product of 3,4-dimethylbenzaldehyde as it is.

[0030] <Aldol condensation step> The method for producing an aldehyde of the present invention has, as the first step, an aldol condensation step of aldol-condensing the aldehyde represented by the formula (3) and propionaldehyde.

[0031] For the aldol condensation reaction of this step, it is preferable to use a basic compound as a catalyst. Examples of the basic compound used as a catalyst include sodium hydroxide, potassium hydroxide, sodium bicarbonate, or a mixture thereof. The amount of the basic compound is preferably 0.05 equivalent or more, more preferably 0.1 equivalent or more, still more preferably 0.2 equivalent or more, and preferably 3 equivalents or less, more preferably 1 equivalent or less, still more preferably 0.5 equivalent or less, based on 1 equivalent of dimethylbenzaldehyde as a raw material.

[0032] The addition amount of propionaldehyde is preferably 0.5 equivalent or more, more preferably 0.8 equivalent or more, and preferably 1.5 equivalents or less, more preferably 1.1 equivalents or less, based on 1 equivalent of dimethylbenzaldehyde as a raw material. The addition of propionaldehyde is preferably carried out sequentially or continuously over time, for example, preferably added dropwise.

[0033] The aldol condensation reaction in this step is preferably carried out in a solvent. Examples of the solvent include various water-miscible organic solvents. Specifically, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, allyl alcohol, ethylene glycol, propylene glycol, and diethylene glycol are preferably exemplified, and methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, ethylene glycol, propylene glycol, and diethylene glycol are more preferable.

[0034] The reaction temperature in the aldol condensation reaction of this step is not particularly limited, but from the viewpoint of the reaction rate, it is preferably 0°C or higher, more preferably 10°C or higher, and from the viewpoint of suppressing side reactions, it is preferably 50°C or lower, more preferably 40°C or lower, still more preferably 30°C or lower. The reaction time is not particularly limited and may be any time sufficient for the condensation to occur, but is preferably 10 minutes or more, more preferably 30 minutes or more, still more preferably 1 hour or more, and preferably 24 hours or less, more preferably 12 hours or less, still more preferably 6 hours or less, and even more preferably 3 hours or less.

[0035] The reaction can be stopped by neutralization. For example, the reaction can be stopped by adding an acid such as acetic acid.

[0036] Also, the method for isolating the intermediate represented by the formula (5) and the intermediate (3-(dimethylphenyl)-2-methylpropenal) represented by the formula (5b) from the solution after the reaction is not particularly limited, and liquid separation, extraction operations, and distillation purification may be appropriately combined. For example, a low-polarity or non-polar organic solvent is added to the solution after the reaction, the intermediate is transferred to the oil phase, the obtained oil phase is dried with, for example, magnesium sulfate, and then the filtrate obtained by filtration is concentrated and further purified by distillation to isolate it.

[0037] <Hydrogenation step> The method for producing the aldehyde of the present invention has a hydrogenation step after the aldol condensation step to obtain the aldehyde represented by the formula (4).

[0038] This step is a step of hydrogenating the intermediate represented by the formula (5) and the intermediate represented by the formula (5b) obtained by the aldol condensation reaction to obtain the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) which are the target products. The method of hydrogenation is not particularly limited, but can be carried out by a known method using a hydrogenation catalyst.

[0039] The hydrogenation catalyst is not particularly limited, and known catalysts can be used. For example, supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.; so-called Ziegler-type hydrogenation catalysts using transition metal salts such as organic acid salts or acetylacetone salts of Ni, Co, Fe, Cr, etc. and reducing agents such as organoaluminum; homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, Zr, etc. can be used.

[0040] From the viewpoints of suppressing reactivity and side reactions, the temperature of the hydrogenation reaction in this step is preferably 0 °C or higher, more preferably 10 °C or higher, still more preferably 20 °C or higher, and is preferably 150 °C or lower, still more preferably 100 °C or lower. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.01 MPaG or higher, more preferably 0.03 MPaG or higher, still more preferably 0.05 MPaG or higher, and is preferably 10 MPaG or lower, more preferably 3 MPaG or lower, still more preferably 1 MPaG or lower, even more preferably 0.5 MPaG or lower. The reaction time is not particularly limited, but is preferably 3 minutes or longer, more preferably 10 minutes or longer, still more preferably 30 minutes or longer, and is preferably 24 hours or shorter, more preferably 12 hours or shorter, still more preferably 8 hours or shorter.

[0041] The hydrogenation reaction may be carried out in the presence of a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the hydrogenation reaction, but examples include hydrocarbon solvents such as aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. These may be used alone or in combination of two or more.

[0042] The method for isolating and purifying the aldehyde represented by the formula (1), the aldehyde represented by the formula (2), or a mixture thereof, which is the target product, from the solution after the reaction is not particularly limited, and a known method may be appropriately selected and carried out. Specifically, filtration, chromatography, distillation purification, etc. are exemplified, and by appropriately combining these for purification, a highly pure target aldehyde or aldehyde composition can be obtained.

[0043] The aldehyde composition containing both the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) obtained in this way has a fresh, marine-like floral and green-like fragrance, is useful as a fragrance, and is further useful as a raw material for a compounded fragrance (fragrance composition). Also, the aldehyde represented by the formula (1) is useful as a fragrance and is also useful as a raw material for a compounded fragrance.

[0044] Note that by further proceeding with the hydrogenation reaction in this step, an alcohol represented by the following formula (6) can also be obtained as shown by the following reaction formula. By containing a small amount of the alcohol represented by the formula (6) in the obtained aldehyde or composition, a more marine feeling can be imparted to the fragrance.

Chemical formula

[0045] <Other production methods> The aldehyde represented by the following formula (1) and the aldehyde composition containing the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2) may be obtained by a method other than the above production method. For example, as represented by the following reaction formula, after synthesizing an acetoxy enol intermediate by the reaction of ortho-xylene and 2-methyl-3,3-diacetoxypropene, a method of synthesizing by hydrolysis may also be used.

Chemical formula

[0046]

Chemical Formula

Examples

[0047] The present invention will be specifically described based on the examples shown below, but the present invention is not limited by these examples.

[0048] <Analysis of Composition> The composition in each step described later, the composition of the product, and the composition of the composition were determined by creating a calibration curve using gas chromatography (GC-2010Plus, manufactured by Shimadzu Corporation) with n-decane (reagent grade, manufactured by Fujifilm Wako Pure Chemical Corporation) as an internal standard substance. As the capillary column, HR-1701 (inner diameter 0.32 mmφ, length 30 m) manufactured by Agilent Technologies was used. The temperature rising program was to raise the temperature from 100 °C to 280 °C at a rate of 5 °C / min and hold for 30 minutes.

[0049] <NMR Spectrum Analysis> Apparatus: Varian NMR System PS600 600 MHz Solvent: deuterated chloroform (CDCl3) Measurement Mode: 1 H, 13 C Internal Standard Substance: tetramethylsilane (TMS)

[0050] <Evaluation of Aroma and Fragrance Tone> The aldehyde compositions and the scents and fragrance notes of the fragrance compositions obtained in the examples and comparative examples were evaluated by impregnating filter paper with a width of 8 mm and a length of 15 cm and having professional panelists smell them.

[0051] <Raw materials> The following raw materials were used in the examples and comparative examples. 3,4-Dimethylbenzaldehyde: manufactured by Mitsubishi Gas Chemical Company, Inc. 2,3-Dimethylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd. Propionaldehyde: manufactured by FUJIFILM Wako Pure Chemical Corporation Methanol: special grade reagent manufactured by FUJIFILM Wako Pure Chemical Corporation Heptane: special grade reagent manufactured by FUJIFILM Wako Pure Chemical Corporation 50% Sodium hydroxide: manufactured by FUJIFILM Wako Pure Chemical Corporation Acetic acid: manufactured by FUJIFILM Wako Pure Chemical Corporation Sodium carbonate: manufactured by FUJIFILM Wako Pure Chemical Corporation 10% Palladium-carbon catalyst: manufactured by N.E. Chemcat Corporation, water-containing product, PE type n-Decane: manufactured by FUJIFILM Wako Pure Chemical Corporation

[0052] <Production of aldehyde> Example 1 (3-(3,4-Dimethylphenyl)-2-methylpropanal (Formula (1))) (Aldol condensation step) A round-bottom flask with an internal volume of 500 mL equipped with a stirring device, a thermometer, and a dropping funnel was charged with methanol (100.0 g), a 50% aqueous sodium hydroxide solution (14.3 g), and 3,4-dimethylbenzaldehyde (purity 99.95% by mass, 2,3-dimethylbenzaldehyde content 0.01% by mass, 100.0 g). After cooling to 15°C with stirring, propionaldehyde (43.6 g) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was held at 15°C for 1 hour to complete the reaction. Acetic acid (10.8 g) was added for neutralization, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation (116 - 120°C / 2 torr) to obtain an intermediate solution containing 3-(3,4-dimethylphenyl)-2-methylpropenal (Formula (5)) as the intermediate.

[0053] (Hydrogenation step) The intermediate solution (64.0 g) obtained in the aldol condensation step, a 5% aqueous sodium carbonate solution (30.0 g), and a 10% palladium-carbon catalyst (manufactured by N.E. Chem. Cat., water-containing product, PE type, 1.0 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature by a jacket, and stirred at 75°C and a hydrogen pressure of 0.4 MPa for 6 hours to carry out a hydrogenation reaction. The reaction solution was filtered to remove the catalyst, heptane was added, and the aqueous phase was separated by liquid separation. Next, heptane was distilled off to obtain a crude composition. The crude composition was rectified at 10 torr using a rectification column with 20 theoretical plates, and 3-(3,4-dimethylphenyl)-2-methylpropanal (Formula (1)) (21.0 g, containing 0.01% by mass of 3-(2,3-dimethylphenyl)-2-methylpropanal (Formula (2))) was obtained as a fraction at 125 - 126°C. The results of NMR spectrum measurement are shown below. The results of the aroma and fragrance evaluation of the obtained aldehyde are shown in Table 1.

[0054] [Results of NMR spectrum measurement of 3-(3,4-dimethylphenyl)-2-methylpropanal (Formula (1))] 11H NMR (600 MHz, CDCl3) δ 1.08 (3H, d, J = 7.2 Hz), 2.23 (3H, s), 2.24 (3H, s), 2.54 (1H, dd, J = 13.8 Hz, 8.4 Hz), 2.63 - 2.67 (1H, m), 3.01 (1H, dd, J = 13.8 Hz, 6.0 Hz), 6.90 (1H, dd, J = 7.5 Hz, 1.5 Hz), 6.94 (1H, s), 7.05 (1H, d, J = 7.8), 9.71 (1H, s) 13 13C NMR (150 MHz, CDCl3) δ 13.3, 19.3, 19.8, 36.3, 48.1, 126.3, 129.7, 130.3, 134.6, 136.1, 136.7, 204.7

[0055] Production Example 1 (3-(2,3-dimethylphenyl)-2-methylpropanal (Formula (2))) Except that 2,3-dimethylbenzaldehyde (purity 99.0%, 25.0 g) was used instead of 3,4-dimethylbenzaldehyde, in the same manner as in Example 1, 3-(2,3-dimethylphenyl)-2-methylpropanal (Formula (2)) (9.0 g, containing 0.08% by mass of 3-(3,4-dimethylphenyl)-2-methylpropanal (Formula (1))) was obtained. The results of NMR spectrum measurement are shown below. The results of the obtained aldehyde aroma and flavor evaluation are shown in Table 1.

[0056] [Results of NMR Spectrum Measurement of 3-(2,3-dimethylphenyl)-2-methylpropanal (Formula (2))] 1 1H NMR (600 MHz, CDCl3) δ 1.10 (3H, d, J = 7.2 Hz), 2.21 (3H, s), 2.28 (3H, s), 2.56 - 2.65 (2H, m), 3.14 (1H, dd, J = 13.8 Hz, 6.0 Hz), 6.97 (1H, dd, J = 6.3 Hz, 2.1 Hz), 7.02 - 7.05 (2H, m), 9.72 (1H, s) 13 13C NMR (150 MHz, CDCl3) δ 13.5, 15.3, 20.8, 34.6, 47.1, 125.4, 127.9, 128.3, 134.6, 136.9, 137.2, 204.6

[0057] Production Example 2 (3-(3,4-Dimethylphenyl)-2-methylpropenal (Formula (5))) (Aldol Condensation Step) Into a 500 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, methanol (100.0 g), 50% aqueous sodium hydroxide solution (14.3 g), 3,4-dimethylbenzaldehyde (purity 99.2% by mass, 2,3-dimethylbenzaldehyde content 0.69% by mass, 100.0 g) were charged. After cooling to 15°C with stirring, propionaldehyde (43.6 g) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was held at 15°C for 1 hour to complete the reaction. Acetic acid (10.8 g) was added for neutralization, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation (116 - 120°C / 2 torr), and further subjected to rectification using a rectification column with 20 theoretical plates to obtain 3-(3,4-dimethylphenyl)-2-methylpropenal (Formula (5)) (10.0 g, purity 98.08% by mass).

[0058] <Production of Aldehyde Composition> Example 2 (Aldol Condensation Step) A round-bottom flask with an internal volume of 500 mL equipped with a stirring device, a thermometer, and a dropping funnel was charged with methanol (100.0 g), a 50% aqueous sodium hydroxide solution (14.3 g), and 3,4-dimethylbenzaldehyde (purity 99.2% by mass, 2,3-dimethylbenzaldehyde content 0.69% by mass, 100.0 g). After cooling to 15°C with stirring, propionaldehyde (43.6 g) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was held at 15°C for 1 hour to complete the reaction. Acetic acid (10.8 g) was added for neutralization, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation (116 - 120°C / 2 torr) to obtain an intermediate solution containing 92.2% of 3-(3,4-dimethylphenyl)-2-methylpropenal (formula (5)) and 0.7% of 3-(2,3-dimethylphenyl)-2-methylpropenal (formula (5b)) as the intermediate.

[0059] (Hydrogenation step) The intermediate solution (64.0 g) obtained in the aldol condensation step, a 5% aqueous sodium carbonate solution (30.0 g), and a 10% palladium-carbon catalyst (manufactured by N.E. Chemcat, water-containing product, PE type, 1.0 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature by a jacket. The mixture was stirred at 75°C and a hydrogen pressure of 0.4 MPa for 6 hours to carry out a hydrogenation reaction. The reaction solution was filtered to remove the catalyst, heptane was added, and the aqueous phase was separated by liquid separation. Next, heptane was distilled off to obtain a crude composition (3-(3,4-dimethylphenyl)-2-methylpropanal purity 91.0%). The crude composition was rectified at 10 torr using a rectification column with 20 theoretical plates, and an aldehyde composition (20.0 g) containing 3-(3,4-dimethylphenyl)-2-methylpropanal (formula (1)) and 3-(2,3-dimethylphenyl)-2-methylpropanal (formula (2)) was obtained as a fraction at 125 - 126°C. The composition of the obtained aldehyde composition and the results of the aroma and fragrance evaluation are shown in Table 1.

[0060] Examples 3 - 4 and Comparative Example 1 To the aldehyde composition obtained in Example 2, the aldehyde obtained in Production Example 1 and the aldehyde obtained in Production Example 2 were added so that each component had the ratio shown in Table 1, and each aldehyde composition was obtained. Table 1 shows the composition of the obtained aldehyde composition and the results of the aroma and fragrance evaluation.

[0061]

Table 1

[0062] Example 5 and Comparative Example 2 (Floral Fruity-like fragrance composition (for detergents)) To the compounded fragrance base shown in Table 2, the aldehyde composition obtained in Example 2 and linalool (Lilial, 3-(p-tert-butylphenyl)-2-methylpropanal) were each added so as to be 3.5% by mass, and the aroma and fragrance evaluation was carried out.

[0063]

Table 2

[0064] Compared with the fragrance composition of Comparative Example 2, the fragrance composition of Example 5 had an increased Heliotrope-like sweetness and Floral feeling.

[0065] Example 6 and Comparative Example 3 (Fruity Floral-like fragrance composition (for body care)) To the compounded fragrance base shown in Table 3, the aldehyde composition obtained in Example 2 and helional (Helional, 3-(3,4-methylenedioxyphenyl)-2-methylpropanal) were each added so as to be 2.5% by mass, and the aroma and fragrance evaluation was carried out.

[0066]

Table 3

[0067] Compared with the fragrance composition of Comparative Example 3, the fragrance composition of Example 6 had a stronger potency, an increased Floral note, and a greater volume.

[0068] Example 7 and Comparative Example 4 (Floral - Green - like fragrance composition (for body care)) To the formulated fragrance base shown in Table 4, the aldehyde composition obtained in Example 2 and Bourgeonal (3-(4 - tert - butylphenyl)propanal) were each added so as to be 3% by mass, and the aroma and fragrance tone were evaluated.

[0069]

Table 4

[0070] Compared with the fragrance composition of Comparative Example 4, the fragrance composition of Example 7 had an increased clean White Floral note and a wider range of fragrance.

[0071] Example 8 and Comparative Example 5 (Floral - Green - like fragrance composition (for fabric care)) To the formulated fragrance base shown in Table 5, the aldehyde composition obtained in Example 2 and Bourgeonal (3-(4 - tert - butylphenyl)propanal) were each added so as to be 12% by mass, and the aroma and fragrance tone were evaluated.

[0072]

Table 5

[0073] The fragrance composition of Comparative Example 5 had a strong Aldehyde note, while the fragrance composition of Example 8 had an increased White Floral note and a well - integrated and sophisticated fragrance.

[0074] From the results of the examples, it can be seen that the aldehyde composition of the present invention has a fresh marine-like floral and green-like fragrance, and thus is useful as a perfume. Furthermore, when blended with a compounded perfume, the floral feeling and heliotrope-like sweetness are enhanced, and it can be seen that it is also useful as a raw material for the compounded perfume. In addition, since the aldehyde represented by the formula (1) of the present invention also has a marine-like floral fragrance, it can be seen that it is useful as a perfume.

Claims

1. containing an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), A perfume composition in which the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) and the aldehyde represented by formula (2) is 96 / 4 to 99.97 / 0.

03. 【Chemical Formula 1】

2. An aldehyde production method having an aldol condensation step of aldol condensing dimethylbenzaldehyde represented by the following general formula (3) and propionaldehyde, and a hydrogenation step in this order to obtain an aldehyde represented by the following general formula (4). 【Chemical Formula 3】

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